Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐Schiff base complex, [MnL(OH₂)](ClO₄) ( 1 ) (H₂L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode Mn^III EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement.     

A versatile protocol for the preparation of substituted 1- and 2-naphthyl piperazines from aminonaphthols

Aminonaphthols are easily transformed into a variety of 1- and 2-naphthyl piperazines using a sequence of diazotization, iodide substitution and Pd(0) catalyzed coupling reactions.     

Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

Sur le groupe des homographies et des antihomographies d'une variable complexe

Sans résumé     

Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

On the Physical Origin of Long-Ranged Fluctuations in Fluids in Thermal Nonequilibrium States

Thermodynamic fluctuations in systems that are in nonequilibrium steady states are always spatially long ranged, in contrast to fluctuations in thermodynamic equilibrium. In the present paper we consider a fluid subjected to a stationary temperature gradient. Two different physical mechanisms have been identified by which the temperature gradient causes long-ranged fluctuations. One cause is the presence of couplings between fluctuating fields. Secondly, spatial variation of the strength of random forces, resulting from the local version of the fluctuation-dissipation theorem, has also been shown to generate long-ranged fluctuations. We evaluate the contributions to the long-ranged temperature fluctuations due to both mechanisms. While the inhomogeneously correlated Langevin noise does lead to long-ranged fluctuations, in practice, they turn out to be negligible as compared to nonequilibrium temperature fluctuations resulting from the coupling between temperature and velocity fluctuations.     

Poincaré-Hopf inequalities

In this article the main theorem establishes the necessity and sufficiency of the Poincaré-Hopf inequalities in order for the Morse inequalities to hold. The convex hull of the collection of all Betti number vectors which satisfy the Morse inequalities for a pre-assigned index data determines a Morse polytope defined on the nonnegative orthant. Using results from network flow theory, a scheme is provided for constructing all possible Betti number vectors which satisfy the Morse inequalities for a pre-assigned index data. Geometrical properties of this polytope are described.

     

Fermions in Odd Space-Time Dimensions: Back to Basics

It is a well-known feature of odd space-time dimensions d that there exist two inequivalent fundamental representations A and B of the Dirac gamma matrices. Moreover, the parity transformation swaps the fermion fields living in A and B. As a consequence, a parity-invariant Lagrangian can only be constructed by incorporating both the representations. Based upon these ideas and contrary to long-held belief, we show that in addition to a discrete exchange symmetry for the massless case, we can also define chiral symmetry provided the Lagrangian contains fields corresponding to both the inequivalent representations. We also study the transformation properties of the corresponding chiral currents under parity and charge-conjugation operations. We work explicitly in 2 + 1 dimensions and later show how some of these ideas generalize to an arbitrary number of odd dimensions.     

The multiple-scale wave equation

An analytic and numerical study of the behavior of the linear nonhomogeneous wave equation of the form ε²u_tt = Δu + tf with high wave speed (ε 1) is carried out. This study was initially motivated by meteorological observations which have indicated the presence of large spatial scale gravity waves in the neighborhood of a number of summer and winter storms, mainly from visible images of ripples in clouds in satellite photos. There is a question as to whether the presence of these waves is caused by the nearby storms. Since the linear wave equation is an approximation to the full system describing pressure waves in the atmosphere, yet is considerably more tractable, we have chosen to analyze the behavior of the linear nonhomogeneous wave equation with high wave speed. The analysis is shown to be valid in one, two, and three space dimensions. Partly because of the high wave speed, the solution is known to consist of behavior which changes on two different time scales, one rapid and one slow. Additionally, because of the presence of the nonhomogeneous forcing term tf, we show that there is a component of the solution which will vary only on a very large spatial scale. Since even the linearized wave equation can give rise to persistent large spatial scale waves under the right conditions, the implication is that certain storms could be responsible for the generation of large-scale waves. Numerical simulations in one and two dimensions confirm analytic results.